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Publication numberUS3597434 A
Publication typeGrant
Publication dateAug 3, 1971
Filing dateOct 17, 1967
Priority dateOct 17, 1967
Publication numberUS 3597434 A, US 3597434A, US-A-3597434, US3597434 A, US3597434A
InventorsMax A Weaver
Original AssigneeEastman Kodak Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Bis-beta,beta-di-cyanovinylenetetrahydroquinoline compounds
US 3597434 A
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Description  (OCR text may contain errors)

fihldgd Patented Aug. 3, 19?]! 3,597,434 BlS-ligfl-Dll-CYANOVHNYLENETETRA- HYDROQUINUHNE CGMPOUNDS Max A. Weaver, Kingsport, Tenn, assignor to Eastman Kodak Company, Rochester, NY.

No Drawing. Filed. Oct. 17, 1967, Sort. No. 675,799 lint. Cl. C(Wd 33/10 Ufi. Cl. 260287R 4 Claims This invention relates to certain novel methine compounds and, more particularly, to bis-methine compounds which are useful as dyes for hydrophobic textile materials.

The bis-methine compounds of the invention are characterized by the general formula NC El II II I (I) C=HCRI I-R XCR O-XR -NR-CHO Y Y wherein R and R individually are the same or different and each represents a p-phenylene group; R and R individually are the same or different and each represents a lower alkyl group, a cycloalkyl group or a phenyl group;

R R R 1t and Janare the same or different and each, when taken collectively, represents a 1,2,3,4-tetrahydroquinolin-1,6- diyl group;

R and R are the same or different and each represents a lower alkylene group;

R represents lower alkylene, alkylene containing a sulfur, oxygen or nitrogen atom in the main chain, vinylene, ethylene, a cycloakylene group, lower cycloakylenedialkylene group, a phenylene group, or a naphthylene p;

X represents oxygen, or nitrogen, e.g.

where R is hydrogen or lower alkyl; and

Y represents cyano, lower alkoxycarbonyl, carbamoyl, N-

lower alkylcarbarnoyl, N,N-di-lower alkylcarbarnoyl, lower alkylsulfonyl, or a phenylsulfonyl group.

The bis-methine compounds of the invention give yellow dyeings having excellent fastness when applied to hydrophobic textile fibers, yarns and fabrics by conventional means. Cellulose acetate, polyamide, modacrylic and polyester fibers are illustrative of the hydrophobic textile materials which can be dyed with the compounds of the invention. The compounds are water insoluble and therefore can be applied to hydrophobic textile materials by methods well known in the art of disperse dyes. Coloration or" such textile materials can also be eflfected by incorporating the novel compounds into the dope or melt prior to spinning and the spinning the fiber as usual. The compounds of the invention exhibit exceptionally good fastness to sublimation on polyester fibers.

The p-phenylene groups which R and R can represent can be substituted or unsubstituted. Typical of the pphenylene groups represented by R and R are p-phenylene, 3-methyl-4-phenylene, 3-chloro-4-phenylene, 3- bromo-4-phenylene, 3-methoxy-4-phenylene, Z-methoxy-S- chloro-4-phenylene, 3-ethyl-4-phenylene, 3-acetamido-4- phenylene, 2-acetamido-5-methyl 4 phenylene, 2,5-di methoxy-4phenylene, etc. The designation of the position of the substituents on the p-phenylene groups represented by R and R is made with reference to the aniline intermediates, i.e. the anilino nitrogen atom is at the 1 position. A preferred group of the p-phenylene groups represented by R and R have the formula wherein Z represents hydrogen, lower alkyl, e.g. methyl, ethyl, butyl; lower alkoxy, e.g. methoxy, ethoxy, propoxy, butoxy; lower alkanoylamino, e.g. acetamido, propionamido, butyramido; lower alkylsulfonamido, e.g. methylsulfonamido, ethylsulfonamido; phenylsulfonamido; phenylsulfonamido substituted with lower alkyl, e.g. p-tolylsulfonamido, lower alkoxy, e.g. p-anisylsulfonamido, or halogen, e.g. p-chlorophenylsulfonamido, p-bromophenylsulfonamido; lower alkoxycarbonylamino, e.g. ethoxycarbonylamino; halogen, e.g. chloro, bromo, benzamido; and n represents 1 or 2. When n is 2, Z can be the same or different.

The alkyl groups which R and R can represent can be straight or branch chain, unsubstituted or substituted lower alkyl. As used herein to describe a substituent, lower refers to an alkyl moiety having up to about 4 carbon atoms. Typical alkyl groups represented by R are methyl, ethyl, propyl, isopropyl, butyl, hydroxyalkyl, e.g. ,B-hydroxyethyl, 2,3-dihydroxypropyl; lower alkoxyalkyl, e.g. fi-methoxyethyl; nitroalkyl, e.g. fl-nitroethyl; cyanoalkyl, e.g. ,B-cyanoethyl; cyanoalkoxyalkyl, e.g. fi-cyanoethoxyethyl; lower alkanoyloxyalkyl, e.g. B-acetoxyethyl; lower alkoxycarbonylalkyl, e.g. fi-ethoxycarbonylethyl; haloalkyl, e.g. ,B-chloroethyl, gamma-chloropropyl, {3- bromethyl; hydroxyhalogenoalkyl, e.g. gamma-chloro-flhydroxypropyl; lower alkanoylaminoal'kyl, e.g. B-acetamidoethyl; carbamoylalkyl, e.g. fl-carbamoylethyl; N- lower alkylcarbamoylalkyl, e.g. B-N-methylcarbamoylethyl; N-phenylcarbamoyloxyalkyl, e.g. B-N-phenylcarbamoylethyl; lower alkylsulfonylalkyl, e.g. B-methylsulfonylethyl; arylalkyl, e.g. benzyl; phenoxyalkyl, e.g. [3- phenoxyethy; lower al-kylsulfonamidoalekyl, e.g. methylsulfonamidoethyl; N-phenylcarbamoyloxyalkyl; lower dicarboximidoalkyl, e.g. succinimidoethyl, etc. Although the alkyl groups represented by R and R are characterized as lower alkyl, when the alkyl group is substituted by a carbon containing substituent, e.g. alkoxy, the preferred substituted alkyl group can contain up to about 8 carbon atoms, e.g. delta-butoxybutyl.

The phenyl groups that R and R can represent include, for example, phenyl and phenyl substituted with lower alkyl, lower alkoxy, nitro, halogen, etc. Illustrative of such groups are phenyl, p-tolyl, m-nitrophenyl, o,p-dichlorophenyl, and p-anisyl. Cyclohexyl is typical of the cycloalkyl groups which R and R can represent.

The l,2,3,4-tetrahydroquinoline group which R and R and R and R together with their common nitrogen atom, can represent can be unsubstituted or substituted. The tetrahydroquinoline groups are attached to the cyanomethylidene groups at the 6 position and to the substituents R and R at the 1 position as is indicated by Formula 1. Examples of the various substituents which can be present on the tetrahydroquinoline group include alkyl, alkoxy, halogen, dialkylamino, phenyl, alkanoyloxy, halogen, alkylsulfonamido, and alkanoylamino. A preferred group of tetrahydroquinolines which R: R RN- and 1\IR8 can collectively represent have the formula wherein Q, Q and Q are the same or different and each represent hydrogen or lower alkyl;

Q represents hydrogen, lower alkyl, lower alkoxy, halogen, hydroxy, or lower alkanoyloxy;

Q represents hydrogen, lower alkyl, lower alkoxy, halogen, or, when Q represents hydrogen or alkyl, phenyl;

Q represents hydrogen, lower alkyl, lower alkoxy, halogen, lower alkanoylamino, lower alkylsulfonamido, lower dialkylamino, or, when Q represents hydrogen or alkyl, phenyl;

Q represents hydrogen, lower alkyl, lower alkoxy, or

halogen.

The alkylene groups represented by R R and R can be straight or branched chain, unsubstituted or substituted lower alkylene. Examples of the alkylene groups represented by R are ethylene, propylene, isopropylene, nbutylene, isobutylene, haloalkylene, e.g. 2-chloropropylene, Z-bromopropylene, chloroethylene, hydroxyalkylene, e.g. Z-hydroxyprop-ylene, hydroxyethylene, lower alkanoylalkylene, e.g. Z-acetoxypropylene, etc.

The alkylene groups represented by R in which an oxygen, sulfur, or nitrogen atom is present can contain up to about 6 carbon atoms. These groups have the general formula R AR wherein R and R are the same or diiferent and each represents straightor branch-chain alkylene having up to about 3 carbon atoms and A represents oxygen, sulfur, sulfonyl or NR wherein R is hydrogen or lower alkyl. Examples of such alkylene groups include CHzCHgSCHzCH2-,

The phenylene groups represented by R can be 0, m, or p-phenylene which can be unsubstituted or substituted, for example, with lower alkyl, lower alkoxy, halogen, nitro, cyano, lower alkanoylamino, lower alkylsulfonamido, lower alkanoyloxy, etc. The groups described above relative to the definition of R and the ortho and meta analogs thereof are typical of the phenylene groups represented by R Cyclohexylene, including 1,4-, 1,3-, and 1,2-cyclohexylene are representative of the cycloalkylene groups which R can represent. Typical cyclohexylenedialkylene groups that R can represent include 1,4-cyclohexylenedimethylene, l,3-cyclohexylenedimethylene, and 1,2 cyclohexylenedimethylene. 1,4 naphthylene, 1,2- naphthylene, and 1,8-naphthylene are illustrative of the naphthylene groups represented by R Such naphthylene groups also include naphthylene substituted, for example, with the groups that can be present on the substituted phenylene groups represented by R Typical lower alkoxycarbonyl groups represented by Y include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, etc. Examples of the lower alkylsulfonyl groups which Y can represent are methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, etc. The phenyl group of the phenylsulfonyl groups which Y can represent can be unsubstituted or substituted, for example, with lower alkyl, lower alkoxy,

halogen, etc. Examples of the substituted phenylsulfonyl groups which Y can be are p-tolylsulfonyl, p-anisylsulfonyl, p-chlorophenylsulfonyl, p-bromophenylsulfonyl, etc. Typical lower alkyl substituted carbamoyl groups are N-methylcarbamoyl, N-ethylcarbamoyl, N-propylcarbamoyl, N-butylcarbamoyl, N,N-dimethylcarbamoyl, N,N-diethylcarbamoyl, N,N-dipropycarbamoyl, etc.

Particularly preferred compounds of the invention have the general formulas R and R are lower alkyl;

R and R are lower alkylene, especially ethylene;

R is lower alkylene or 0-, m-, or p-phenylene;

R is hydrogen, lower alkyl, lower alkoxy, halogen, or

lower alkanoylamino;

R is hydrogen, lower alkyl, lower alkoxy, or halogen;

and

Q, Q Q and Q are the same or different and each represents hydrogen or lower alkyl.

As is well known in the art, the color of the compounds of the invention is attributable to the conjugated system of the cyanomethylidenephenylamino and the cyanomethylidenetetrahydroquinoline moieties of the novel compounds. Thus the substituents present on the groups represented by R, R R R R R and R and the group represented by Y, as these substituents and groups are defined aboue, do not materially affect the primary usefulness of the compounds, i.e., the ability of the compounds to dye hydrophobic fibers. As can be seen from the subsequent examples, the substituents mentioned above function primarily as auxochrom groups to control the shade of the compounds of the invention.

The bis-methine compounds of the invention are prepared by reacting an aminoalkyl compound or hydroxyalkyl compound represented by the formulae with a dicarboxylic acid, or lower alkyl ester thereof, having the formula wherein R, R R R R R R and X are defined above. Thus, to prepare a symmetrical bis-methine compound, i.e., where R, R and R are the same as R R and R the compounds of Formulae II and III are the same and 2 moles of the aminoalkyl or hydroxyalkyl compound is reacted with 1 mole of an acid of Formula IV to yield the intermediate compound V:

The reaction is carried out in the presence or absence of solvents and with the use eof a catalyst such as sulfuric acid, p-toluenesulfonic acid, tetraisopropyltitanate, etc.

The intermediate compound V is then formylated (e.g. by treating with POCl and dimethylformamide) and the formylated product is reacted with an active methylene compound, e.g. malononitrile, to yield the novel bismethine compound of Formula I.

To prepare the unsymmetrical compounds of the invention, the procedure is essentially the same except that 1 mole of a compound of Formula II is reacted with a dicarboxylic acid anhydride having the Formula and the product obtained is reacted with a compound of Formula III, where the compounds of Formulae II and III are diiferent. The intermediate is then formylated and reacted with an active methylene compound as described above to yield the bis-methine compound of Formula I.

The intermediates useful in preparing the compounds of the invention are commercially available or can be prepared by known procedures.

Representative compounds corresponding to Formulae II and III include N-ethyl-N-fi-hydroxyethyl-m-toluidine, N-ethyl-N-fi-hydroxyethylaniline, N-Z-aminoethyl-N-ethyl-m-toluidine, N-n-butyl-N-B-hydroxyethyl-m-anisidine, N-chloroethyl-N,8-hydroxyethyl-m-chloroaniline, N-methoxyethyl-N-fl-hydroxyethyl-m*chloroaniline, N-cyanoethyl-N-fl-hydroxyethylaniline, N-acetamidoethyl-N-B-hydroxyethylaniline, N-phenoxyethyl-N-B-hydroxyethyl-m-toluidine, N-[i-hydroxyethyl-N-ethoxycarbonylethyl-m-anisidine, N-carbonaminidoethyl-N-Z-aminoethylaniline, N-cyanoethoxyethyl-N-Z-aminoethyl-m-anisidine, N-benzyl-N-2-aminoethyl-m-toluidine, N-phenyl-N-Z-aminoethylaniline, N-succinimidoethyl-N-Z-aminoethylaniline, etc.

Where R and R together with their common nitrogen atom, form a heterocyclic group, representative compounds are l-(2-hydroxyethyl)-2,2,4,7-tetramethyl-1,2,3,4-tetrahydroquinoline,

1-(2-hydroxyethyl)-1,2,3 ,4-tetrahydro quinoline,

1-(2-hydroxyethyl) -2,2,4,7-tetraethyl-1,2,3 ,4-tetrahydroquinoline,

1-(2'aminoethyl)-2,2,4-trimethyl-7-methoxy-l,2,3,4-

tetrahydroquinoline,

1-(2-aminoethyl)-2,2,4-trimethyl-7-chloro-1,2,3,4-

tetrahydroquinoline,

1- (Z-hydroxyethyl -2,2,4-trimethyl-7-ethoxy- 1,2,3 ,4-

tetrahydroquinoline, etc.

Representative compounds corresponding to Formula IV include diethyl succinate, dimethyl glutarate, dimethyl maleate, dimethyl isophthalate, dimethyl terephthalate, dimethyl phthalate, 1,4-cyclohexanedicarboxylic acid, etc.

Typical active methylene compounds utilized in preparing the novel bis-methine compounds of the invention are malononitrile, methylsulfonylacetonitrile, methylcyanoacetate, phenylsulfonylacetonitrile, cyanoacetarnide, etc.

The following examples further illustrate the preparation of representative intermediates and bis-methine compounds of the invention.

EXAMPLE 1 (a) Preparation of bis[Z-(N-ethyl-m-toluidino) ethyl1succinate An amount of 34.8 g. diethyl scccinate, 71.6 g. N-ethyl- N-fi-hydroxyethyl-m-toluidine and 5 drops of titanium tetraisopropoxide are stirred and refluxed together for 3 hrs., allowing ethanol to be removed. The reflux temperature rose from 170 C. to 210 C. during this period, and about 90% of the theoretical amount of ethanol is collected. The product is allowed to cool and a portion is converted into the bis-aldehyde.

(b) Preparation of his [2-(N-ethyl-4-formyl-mtoluidino ethyl 1 succinate An amocnt of 22.0 g. of bis[2-(N-ethyl-m-toluidino) ethyl]succinate is dissolved by stirring in 20 ml. of dry dimethylformamide. The solution is cooled and 10 ml. of phosphorus oxychloride added below 30 C. After heating 1 hr. on the steam bath, the reaction is drowned on an ice-water mixture. This mixture is then made basic with 50% NaOH, resulting in an oily product. The aqueous portion is decanted off and the bis-aldehyde taken up by heating with ml. of ethanol. 0n cooling, the product crystallizes and is collected by filtration, washed with ethanol and air dried. The product melts at -90 C. and one recrystallization from ethanol gives the pure bis-aldehyde melting at -97 C.

(c) Preparation of bis-methine dye An amount of 4.97 g. bis[2-(N-ethyl-4-formyl-m toluidino)ethyl1succinate, 1.32 g. malononitrile, ml. ethanol and 5 drops of piperidine are heated together on steam bath for 30 minutes. The product crystallizes on cooling and is collected by filtration. The crude product is heated to boiling in 100 ml. of ethanol, allowed to cool to about 50 C., filtered, washed with ethanol, and air dried. The yellow dye obtained melts at 152-157 C. and dyes polyester fibers yellow shades of outstanding light and sublimation fastness. The dye has the following structure:

N C CZHS /C:H o N N C (H) (I? 32115, C N C H4o0CI-hCH 0oo mN CII=C I C N CH,

EXAMPLE 2 (a) Preparation of bis[2- ('N-ethyl-m-toluidino) ethyl] isophthalate An amount of 179 g. N-ethyl-N-B-hydroxyethyl-mtoluidine, 97 g. dimethylisophthalate, and 10 drops titanium tetraisopropoxide are refluxed together for 2 hr., allowing the methanol to be removed. The reflux temperature rose from C. to 200 C. during this period. The mixture is then transferred to a distillation flask and low boiling material is removed (-35 g.) until the pot temperature reaches 200 C. at 038 mm. Hg. The product remaining in the flask weighs 213 g., and is a very heavy, viscous liquid.

(b) Preparation of bis [2-(N-ethyl-4formyl-m-toluidino) ethyl] isophthalate An amount of 48.8 g. of bis[2-(N-ethyl-m-toluidino) ethylJisophthalate is dissolved in 50 ml. of dry dimethylformamide. The solution is cooled and 20 ml. POCI added below 35 C. After heating 1%. hr. on the steam bath the reaction is drowned slowly with good stirring into 1 liter of water containing 35 ml. of 50% NaOH and enough ice to keep the mixture at about room temperature. A sticky product results which is washed once by decantation and then taken up in 500 ml. of hot ethanol. On standing at room temperature for several days, the product crystallizes and is collected by filtration, washed with ethanol and air dried; M.P. 89-92" C.

Elemental analysis.Theoretical (percent): C, 70.5; H, 6.7; N, 5.1. =Found (percent): C, 70.5; H, 7.0; N, 5.2.

() Preparation of bis-methine dyes An amount of 2.74 g. bis[2-(N-ethyl-4-formyl-mtoluidino)ethyl]isophthalate, 0.66 g. malononitrile, 3 drops piperidine, and 15 ml. methyl Cellosolve are heated together at 100 C. for 1 hr. The reaction is allowed to cool and the product collected by filtration, washed with ethanol, and air dried. The yellow dye melts at 15816 l C. and dyes polyester fibers yellow shades having excellent light and sublimation fastness. The structure of this dye is: Y

An amount of 1.3 g. bis[2-(N-ethyl-4-formyl-m-toluidino)ethyl]isophthalate, prepared according to Example 2(b), above, 0.60 g. methylsulfonylacetonitrile, 3 drops of piperidine, and 25 ml. ethanol are refluxed together for 2 hr. After allowing to stand overnight at room temperature, the product is filtered, washed with ethanol,

and air dried. The yellow dye has the following structure:

NC $211 (I? \C=HC N--C2H4O C- CHaOzS CH Q COO2H4NOH=C\ EXAMPLE 4 An amount of 1.36 g. bis[2-(N-ethyl-4-forrnyl-m-toluidino)ethyl]isophthalate and 0.50 g. methylcyanoacetate are reacted together using the same conditions of Example 3, to yield the following yellow dye:

NC CzH5 O An amount of 1.36 g. bis[2- (N-ethyl-4-formyl-m-tolui dino)ethyl]isophthalate and 0.90 g. of phenylsulfonylacetonitrile are reacted together as in Example 3, to yield the following yellow dye:

N CzHs fl) EXAMPLE 6 An amount of 1.36 g. bis[2- (N-ethyl-4-formy1-m-toluidino)ethyl]isophthalate and 0.42 g. of 2-cyanoacetamide are reacted as in Example 3 to yield the following yellow dye:

/C=HCNO2H4OC- H N-C H CH3 0 o c-NH,

CH3 ll 0 EXAMPLE 7 (a) Preparation of bis[2-( N-ethylanilino)ethyl] isophthalate An amount of 82.5 g. N-ethyl-Nfl-hydroxyethylaniline, 48.5 g. dimethylisophthalate, and 5 drops titanium tetraisopropoxide are heated together at reflux for 2 hr. The temperature rose from 180 C. to 215 C. during this period as methanol was removed. The product, Which is a viscous liquid, is allowed to cool and is used to prepare the bis-aldehyde.

(b) Preparation of bis[2-(N-ethyl-4-formylanilino) ethyl]isophthalate An amount of 23.0 g. bis[2-(N-ethylanilino)ethyl isophthalate is dissolved in 20 ml. of dry dimethylformamide. The solution is cooled and 10 ml. of phosphorus oxychloride are added below 30 C. After heating for 1 hr. at the reaction is drowned into an ice-water mixture. This is made basic with 50% NaOH and the sticky product is washed by decantation. The product is taken up in 200 ml. ethanol and allowed to stand overnight. The bis-aldehyde crystallizes and is collected by filtration and dried. Recrystallization from ml. ethanol gives the pure aldheyde melting at 102l04 C.

(c) Preparation of bis-methine dye An amount of 2.58 g. bis[2-(N-ethyl-formylanilino) ethyl]isophthalate, 0.6-6 g. malononitrile, 3 drops piperidine, and 25 ml. ethanol are refluxed together for 1 hr. The reaction is allowed to cool and the product is collected by filtration, washed with methanol, and air dried. The dye melts at 171-176 C. and dyes polyester fibers bright, greenish yellow shades possessing excellent light and sublimation fastness. It has the following structure:

9 EXAMPLE 8 (a) Preparation of bis[2-(N-ethyl-m-toluidino)- ethyl]isophthalamide (b) Preparation of bis[2-(N-ethyl-4-formyl-mtoluidino ethyl] isophthalamide An amount of 4.86 g. bis[Z-(N-ethyl-m-toluidino)- ethyl]isophthalamide is stirred with 5 ml. dry dimethylformamide. To this slurry is added 2 ml. phosphorus oxychloride at about C. The reaction mixture is heated 1 hr. on the steam bath, drowned on ice-water, made basic with NaOH, and the product is washed by decantation. The sticky product is recrystallized from ethanol, filtered, and air dried; M.P. l05 C.

(c) Preparation of bis-methine dye An amount of 2.70 g. bis[2-(N-ethyl 4 formyl-mtoluidino)ethyl]isophthalamide, 0.66 g. malononitrile, 3 drops piperidine, and 30 ml. ethanol are refluxed together for 2 hr. The product crystallizes on standing at room temperature for about 2 days, and is collected by filtration, washed with ethanol, and air dried; VLP. 122 128 C. This product dyes polyester fibers deep yellow shades and has the following structure:

NC 0 11 O H 43 N o (3211's 0 N fiNHC2H4N OH=C 0 UN CH3 EXAMPLE 9 (a) Preparation of his [2-(1,2,3,4-tetrahydro-2,2,4,7- tetrarnethyll-quinolyl ethyl] isophthalate An amount of 46.6 g. 1-(2-hydroxyethyl)-2,2,4,7-tetramethyl 1,2,3,4 tetrahydroquinoline, dirnethyl isophthalate (19.4 g.), and 5 drops of titanium tetraisopropoxide are refluxed together for 3 hrs. During this time methanol is removed and the temperature rose from C. to C. This product is used to prepare the bis-aldehyde.

(b) Preparation of bis[2-(6-formyl-1,2,3,4-tetrahydro- 2,2,4,7-tetramethyl-1-quinolyl)ethylJisophthalate An amount of 29.8 g. bis[2-(1{2,3,4-tetrahydro-2,2,4,7- tetramethyl 1 quinolyl)ethylJisophthalate is treated with 20 ml. dry dirnethyl formamide and 10 ml. POCl as illustrated in the preceding examples. The product, after drowning on ice-water mixture and basifying, gives a sticky aldehyde, which does not crystallize.

(c) Preparation of bis-rnethine compound An amount of 2.18 g. bis[2-(6-formy1-1,2,3,4-tetrahydro-2,2,4,7-tetramethyl 1 quinolyl)ethyl]isophthalate, 0.44 g. malononitrile, 3 drops piperidine, and 35 ml. ethanol are refluxed together for 1 hr. The re action mixture is allowed to cool, and the product is 20 collected by filtration, washed with ethanol, and air dried. The dye gives beautiful yellow dyeings on polyester fibers having good light and sublimation fastness. It has the following structure:

UH=C CH S I ON 9.'

CHa I COCHZCHQ The compounds described in the examples of Table l are prepared according to the procedure of Examples The compounds of Table 1 give yellow dyeings of excellent fastness properties on polyester fibers.

TABLE 1 Ex. No. 2 11 R1, R5 R1, R4 x R3 Y 10 3-0113 412m ereon? N [/x u xr't-tt th il ("Il. H I It n s-ctn ont 41inch? o-- l3. Ill ira. M (EH5 'lllal lllg --tl (N 13 The compounds set forth in the examples of Table 2 are prepared according to the procedure of Examples 1-9 and correspond to the general formula:

Y B on The compounds impart yellow shades to, and display 10 excellent fastness properties on, polyester fibers.

following example illustrates a method by which the compounds of the invention can be used to dye hydrophobic textile materials.

EXAMPLE 76 TABLE 2 Substitutents on- Substituents on Ex. No. Ring B Ring A R R X R Ring Ring D Y 48 None None CH2CH2- 0- Q- None None ON 49 2-OH do CH2OH2 O Same as above. 2-CH; d 50 None- 7-01-1 CH2CH2- O 51 2-011 7-OH CH2CH2 NH- OlhCHz- 52 2,2,4-tri-OH None OH2GH2 O CH2CHZ 53 2,2,4-tri-CH CH OHz -O-- CHzCH2 64 CHzCHz- O CH2CH2 2-CH2 55 -CH2CH2 --O-- --OH2CH2 $0113.... 7-01 u 56. CHzCHz- O CH2CH2 2-011 7 .NHCOOH H CN 57 2-CH 7-CH CH2CH2CH2- NH- 2-OH 7- OH; i CN 58 2-CH 7-013 --CH2CH2CH2- -NH- Same asabove. 2-011 7-CH SO2CI{Q 2-0113" 7-OH CH2CHz O- do H H CN 2-0113... 7OH -OH2CH2 -O .,do H 7- OH CN 2,2,4-tri-CH CHzCHz- O- OH2OCH 2-CH 7-CH CN 2-C2H 7 C H CH CH2 O- -CHzCH2- 2-OH 7-CH ON CH2CH2 O CH2CH2- Z-OH H 7-C H1 ON CHzCHz- O CHzCHz- 2-CH 700 1-1 ON 3 CH2CH2- O- OH2CH2 2-CH3 7-0C H1 CN The compounds give yellow dyeings of excellent fastness properties on polyester fibers.

Corp.) are added and 10 grams of a textile fabric made of poly(ethylene terephthalate) polyester fibers are entered. The fabric is worked 10 minutes without heat and then for 10 minutes at 80 C. The dye bath is then brought to the boil and held at the boil for one hour. Following this, the fabric is rinsed in warm water, then scoured in aqueous 0.2% soap, 0.2% soda ash solution. After scouring, the fabric is rinsed with water and dried. When the compounds are used to dye polya'mide textile materials, the above described procedure can be employed except the Tanavol dyeing assistant need not be used. In applying the compounds of the invention to cellulose acetate fibers, the above procedure can be employed, omitting the Tanavol and carrying out the dyeing at 80 C.

Polymeric linear polyester materials of the terephthalate type are illustrative of the linear aromatic polyester tex- The compounds of the invention can be used for dyeing hydrophobic fibers such as linear polyester, cellulose ester, polyamide, etc., fibers in the manner described in U.S.

tile materials that can be dyed with the new compounds of our invention. Examples of such linear polyester materials are those prepared from ethylene glycol and dimeth- Pats. 2,880,050, 2,782,187, 2,757,064, and 3,043,827. The ylterephthalate and those prepared. from 1,4-cyclohexanedimethanol and dimethylterephthalate. Polyester textile materials prepared from 1,4-cyclohexanedimethanol and dimethylterephthalate are more particularly described in U.S. Pat. 2,901,446. Poly(ethylene terephthalate) fibers are described, for example, in U.S. Pat. 2,465,319. The polymeric linear polyester materials disclosed in U.S. Pats. 2,945,010, 2,957,745, and 2,989,363, for example, can be dyed. The linear aromatic polyester materials specifically named have a melting point of at least 200 C.

Examples of the polyamide fibers that can be dyed with the compounds of the invention are those consisting of nylon 66, made by the polymerizaion of adipic acid and hexamethylenediamine, nylon 6, prepared from epsilonaminocaproic acid lactam, and nylon 8. Fibers of cellulose triacetate and partially hydrolyzed cellulose acetate can also be dyed with the compounds of the invention.

The invention has been described in considerable detail with particular reference to certain preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention as described above and as defined in the appended claims.

R and R each is lower alkylene;

R is alkylene of up to about 6 carbon atoms, phenyiene,

lower alkylphenylene, lower alkoxyphenylene or halophenylene; and

Q, Q Q and Q are the same or different and each is hydrogen or methyl.

2. A compound according to claim 1 wherein R reppresents lower alkylene or 0-, m-, or p-phenylene.

3. A compound according to claim 1 wherein R and R each is ethylene; R is ethylene or m-phenylene; and Q, Q Q and Q each is methyl.

4. A compound according to claim 3 having the formula CH; NC\

C=HC- A NC CH 5 I /ON A -on=o l S CN N CH3 (liioCHzHz References Cited UNITED STATES PATENTS 3,247,211 4/1966 Weaver et al. 260287 3,422,133 1/1969 Dale et a]. 260287X 3,504,010 3/1970 Straley et a1. 260287 DONALD G. 'DAUS, Primary Examiner U.S. Cl. X.R.

8-55; 2602409, 283CN, 2835A, 288R, 289R, 429$, 465R, 465D, 465.4, 471R

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3979429 *May 8, 1975Sep 7, 1976Sandoz Ltd.Para-amino-β-cyano-bis-styryl compounds
US4331584 *May 23, 1980May 25, 1982Sumitomo Chemical Company, LimitedStyryl compounds and coloring synthetic resins therewith
US4749772 *Jul 20, 1987Jun 7, 1988Eastman Kodak CompanyPolyester reacted with cyano(meth)acrylate substituted with furanyl or thienyl
US4749773 *Jul 27, 1987Jun 7, 1988Eastman Kodak CompanyCondensation polymers containing methine ultraviolet radiation-absorbing residues and shaped articles produced therefrom
US4749774 *Jul 27, 1987Jun 7, 1988Eastman Kodak CompanyUnsaturated polyesters
US4788121 *Oct 17, 1986Nov 29, 1988Eastman Kodak CompanyElectrostatography
US5260179 *Sep 16, 1992Nov 9, 1993Eastman Kodak CompanyContaining a filter dye in a hydrophilic layer
US5466813 *Jul 20, 1993Nov 14, 1995Eastman Kodak CompanyImine dye and photographic elements containing same
EP0012300A2 *Dec 1, 1979Jun 25, 1980BASF AktiengesellschaftColoured polymeric compounds, process for their preparation and their application to the dyeing of paper
Classifications
U.S. Classification546/165, 560/19, 8/657, 558/403, 8/904, 8/636, 560/154, 8/922, 560/180, 8/924, 560/171, 560/83, 8/932, 560/80
International ClassificationC09B23/14, C07D215/12, C07D215/38, C07D215/14, C07D215/18, C07D215/06, C07D215/20
Cooperative ClassificationY10S8/932, Y10S8/922, Y10S8/904, C07D215/20, C07D215/18, C07C255/00, C07D215/38, C07D215/06, Y10S8/924, C07D215/14, C09B23/143, C07D215/12
European ClassificationC07C255/00, C07D215/06, C07D215/14, C07D215/12, C07D215/20, C09B23/14D, C07D215/38, C07D215/18
Legal Events
DateCodeEventDescription
May 16, 1986ASAssignment
Owner name: CIBA-GEIGY CORPORATION, 444 SAW MILL RIVER ROAD, A
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:EASTMAN KODAK COMPANY;REEL/FRAME:004571/0415
Effective date: 19860321